Source and flux of POC in two subtropical karstic tributaries with contrasting land use practice in the Yangtze River Basin

Elemental (C/N ratio) and C isotope composition (δ¹³C) of particulate organic C (POC) and organic C content (OC) of total suspended solids (TSS) were determined for two subtropical karstic tributaries of the Yangtze River, the Wujiang (the eighth largest tributary) and Yuanjiang (the third largest tributary). For the latter, two headwaters, the karstic Wuyanghe and non-karstic Qingshuijiang were studied. The Wujiang catchment is subject to intensive land use, has low forest coverage and high soil erosion rate. The δ¹³C of POC covered a range from −30.6‰ to −24.9‰, from −27.6‰ to −24.7‰, and from −26.2‰ to −23.3‰ at the low-water stage, while at the high-water stage varied in a span between −28.6‰ and −24.4‰, between −27.7‰ and −24.5‰, and between −27.6‰ and −24.2‰ for the Wujiang, Wuyanghe, and Qingshuijiang, respectively. The combined application of C isotopes, C/N ratio, OC, and TSS analyses indicated that catchment soil was the predominant source of POC for the Wujiang while for the Wuyanghe and Qingshuijiang, in-stream processes supplied the main part of POC in winter and summer. A significant increase in δ¹³C value (1.4‰) of POC was found in the Wujiang during summer, and was attributed to the enhanced soil erosion of the dry arable uplands close to the riverbanks of the main channel. Based on a conservative estimate, POC fluxes were 3.123 × 10¹⁰, 0.084 × 10¹⁰, and 0.372 × 10¹⁰ g a⁻¹ while export rates of POC were 466, 129, and 218 mg m⁻² a⁻¹ for the Wujiang, Wuyanghe, and Qingshuijiang, respectively. The POC export rate for the karstic Wujiang, with intensive land use, was 2–3 higher than that of the karstic Wuyanghe or of the non-karstic Qingshuijiang where soil erosion was minor. Such high values imply rapid degradation of related karstic ecosystems impacted by intensive land use activities, and pose a potential threat to the health of the Three Gorges Reservoir.     

Carbon biogeochemistry of the Betsiboka estuary (north-western Madagascar)

Madagascar’s largest estuary (Betsiboka) was sampled along the salinity gradient during the dry season to document the distribution and sources of particulate and dissolved organic carbon (POC, DOC) as well as dissolved inorganic carbon (DIC). The Betsiboka was characterized by a relatively high suspended matter load, and in line with this, low DOC/POC ratios (0.4–2.5). The partial pressure of CO₂ (pCO₂) was generally above atmospheric equilibrium (270–1530 ppm), but relatively low in comparison to other tropical and subtropical estuaries, resulting in low average CO₂ emission to the atmosphere (9.1 ± 14.2 mmol m⁻² d⁻¹). Despite the fact that C4 vegetation is reported to cover >80% of the catchment area, stable isotope data on DOC and POC suggest that C4 derived material comprises only 30% of both pools in the freshwater zone, increasing to 60–70% and 50–60%, respectively, in the oligohaline zone due to additional lateral inputs. Sediments from intertidal mangroves in the estuary showed low organic carbon concentrations (<1%) and δ¹³C values (average −19.8‰) consistent with important inputs of riverine imported C4 material. This contribution was reflected in δ¹³C signatures of bacterial phospholipid derived fatty acids (i + a15:0), suggesting the potential importance of terrestrial organic matter sources for mineralization and secondary production in coastal ecosystems.     

12,000-Year, preliminary results of the stable nitrogen and carbon isotope record from the Empakai Crater lake sediments, Northern Tanzania

The stable isotope compositions of organic carbon and nitrogen, the contents of organic carbon and nitrogen and C/N ratios for two cores recovered from the Empakai Crater at water depths of 11 and 20 m are used to document climatic changes in northern Tanzania. Eight ¹⁴C AMS dates determined on total organic matter (OM) indicate that the sedimentation rate in this lake is about 30 cm/ka for the late Pleistocene to early Holocene period. There are differences in the δ¹³C values of organic carbon between the two cores, which may be a result of differences in location from the present shoreline and of different water depths. In the deeper-water core the δ¹³C values show a general downcore decrease to the base of the core with a sharp change to lower values of about 4‰ at a depth of 100 cm (8.7 ka). The general trend of downcore decrease in ¹³C values can be attributed either to a systematic decrease in the relative proportion of C₄ type of OM, owing to an increase in precipitation and change in vegetation cover from grassland to forest, or to utilization of isotopically enriched carbon during photosynthesis. The δ¹⁵N values show a general downcore increase with again a sharp change of about 5‰ to lower values at about 8.7 ka. A sharp change of about 5‰ and 4‰ to more depleted values at a depth of 100 cm of both ¹⁵N and ¹³C, respectively, suggests either hiatus or abrupt change in climatic condition from wetter conditions to drier conditions. There is enhanced preservation of OM in the lake as depicted by high mean values of organic carbon and nitrogen at both sites.     

Paleohydrology of the upper Laurentian Great Lakes from the late glacial to early Holocene

Between 10,500 and 9000 cal yr BP, δ¹⁸O values of benthic ostracodes within glaciolacustrine varves from Lake Superior range from − 18 to − 22‰ PDB. In contrast, coeval ostracode and bivalve records from the Lake Huron and Lake Michigan basins are characterized by extreme δ¹⁸O variations, ranging from values that reflect a source that is primarily glacial ( − 20‰ PDB) to much higher values characteristic of a regional meteoric source ( − 5‰ PDB). Re-evaluated age models for the Huron and Michigan records yield a more consistent δ¹⁸O stratigraphy. The striking feature of these records is a sharp drop in δ¹⁸O values between 9400 and 9000 cal yr BP. In the Huron basin, this low δ¹⁸O excursion was ascribed to the late Stanley lowstand, and in the Lake Michigan basin to Lake Agassiz flooding. Catastrophic flooding from Lake Agassiz is likely, but a second possibility is that the low δ¹⁸O excursion records the switching of overflow from the Lake Superior basin from an undocumented northern outlet back into the Great Lakes basin. Quantifying freshwater fluxes for this system remains difficult because the benthic ostracodes in the glaciolacustrine varves of Lake Superior and Lake Agassiz may not record the average δ¹⁸O value of surface water.     

New constraints on the release of noble gases during in vacuo crushing and application to scapolite Br–Cl–I and Ar/Ar age determinations

The release of irradiation-produced noble gas isotopes (³⁸Ar_Cl, ⁸⁰Kr_Br, ¹²⁸Xe_I and ³⁹Ar_K) during in vacuo crushing scapolite has been investigated and is compared to quartz. Three thousand crushing strokes released 98% of fluid inclusion-hosted noble gas from quartz. In comparison, 3000 crushing strokes released only 4% of the lattice-hosted ³⁸Ar_Cl from a scapolite gem. In vacuo crushing released lattice Ar preferentially relative to lattice Kr or Xe and prolonged crushing released 88% of the lattice-hosted noble gas in 96,000 crushing strokes. We suggest fast diffusion pathways generated by crushing are an important noble gas release mechanism and we demonstrate two applications of prolonged in vacuo crushing on irradiated scapolite.Firstly, scapolite molar Br/Cl and I/Cl values are shown to vary over a similar range as crustal fluids. The Cl-rich scapolite gem from Hunza, Pakistan has Br/Cl of 0.5–0.6 × 10⁻³ and I/Cl values of 0.3–2 × 10⁻⁶, that are similar to fluids that have dissolved evaporites. In contrast, three out of four skarn-related scapolites from the Canadian Grenville Province have molar Br/Cl values of 1.5–2.4 × 10⁻³, and I/Cl values of 11–24 × 10⁻⁶, that are broadly consistent with skarn formation by magmatic fluids. The fourth Grenvillian scapolite, with only 0.02 wt% Cl, has an exceptionally elevated molar Br/Cl value of up to 54 × 10⁻³ and I/Cl of 284 × 10⁻⁶. It is unclear if these values reflect the composition of fluids formed during metamorphism or preferential incorporation of Br and I in Cl-poor meionitic scapolite.Secondly, the Grenvillian scapolites give plateau ages of between 830 Ma and 400 Ma. The oldest ages post-date regional skarn formation by 200 Myr, but are similar to feldspar cooling ages in the Province. The age variation in these samples is attributed to a combination of factors including variable thermal history and the presence of mineral sub-grains in some of the samples. These sub-grains control the release of ³⁹Ar_K, ³⁸Ar_Cl and ⁴⁰Ar* during in vacuo crushing as well as the samples ⁴⁰Ar* retentivity in nature. Scapolite is suggested as a possible analogue for K-feldspar in thermochronologic studies.     

Abundance and Chemical Speciation of Phosphorus in Sediments of the Mackenzie River Delta, the Chukchi Sea and the Bering Sea: Importance of Detrital Apatite

Utilizing a sequential extraction technique this study provides the first quantitative analysis on the abundance of sedimentary phosphorus and its partitioning between chemically distinguishable phases in sediments of the Bering Sea, the Chukchi Sea and the Mackenzie River Delta in the western Arctic Ocean. Total sedimentary phosphorus (TSP) was fractionated into five operationally defined phases: (1) adsorbed inorganic and exchangeable organic phosphorus, (2) Fe-bound inorganic phosphorus, (3) authigenic carbonate fluorapatite, biogenic apatite and calcium carbonate-bound inorganic and organic phosphorus, (4) detrital apatite, and (5) refractory organic phosphorus. TSP concentrations in surface sediments increased from the Chukchi Sea (18 μmol g⁻¹ of dried sediments) to the Bering Sea (22 μmol g⁻¹) and to the Mackenzie River Delta (29 μmol g⁻¹). Among the five pools, detrital apatite phosphorus of igneous or metamorphic origin represents the largest fraction (~43%) of TSP. The second largest pool is the authigenic carbonate fluorapatite, biogenic apatite as well as CaCO₃ associated phosphorus (~24% of TSP), followed by the Fe-bound inorganic phosphorus, representing ~20% of TSP. The refractory organic P accounts for ~10% of TSP and the readily exchangeable adsorbed P accounts for only 3.5% of TSP. Inorganic phosphorus dominates all of phosphorus pools, accounting for an average of 87% of the TSP. Relatively high sedimentary organic carbon and total nitrogen contents and low δ¹³C values in the Mackenzie River Delta together with the dominance of detrital apatite in the TSP demonstrate the importance of riverine inputs in governing the abundance and speciation of sedimentary phosphorus in the Arctic coastal sediments.     

Isotopic evidence for temporal variation in proportion of seasonal precipitation since the last glacial time in the inland Pacific Northwest of the USA

Large-scale atmospheric circulation patterns determine the quantity and seasonality of precipitation, the major source of water in most terrestrial ecosystems. Oxygen isotope (δ¹⁸O) dynamics of the present-day hydrologic system in the Palouse region of the northwestern U.S.A. indicate a seasonal correlation between the δ¹⁸O values of precipitation and temperature, but no seasonal trends of δ¹⁸O records in soil water and shallow groundwater. Their isotope values are close to those of winter precipitation because the Palouse receives  75% of its precipitation during winter. Palouse Loess deposits contain late Pleistocene pedogenic carbonate having ca. 2 to 3‰ higher δ¹⁸O values and up to 5‰ higher carbon isotope (δ¹³C) values than Holocene and modern carbonates. The late Pleistocene δ¹⁸O values are best explained by a decrease in isotopically light winter precipitation relative to the modern winter-dominated infiltration. The δ¹³C values are attributed to a proportional increase of atmospheric CO₂ in soil CO₂ due to a decrease in soil respiration rate and ¹³C discrimination in plants under much drier paleoclimate conditions than today. The regional climate difference was likely related to anticyclonic circulation over the Pleistocene Laurentide and Ice Sheet.     

The sources and evolution of mineralising fluids in iron oxide–copper–gold systems, Norrbotten, Sweden: Constraints from Br/Cl ratios and stable Cl isotopes of fluid inclusion leachates

We have analysed the halogen concentrations and chlorine stable isotope composition of fluid inclusion leachates from three spatially associated Fe-oxide ± Cu ± Au mineralising systems in Norrbotten, Sweden. Fluid inclusions in late-stage veins in Fe-oxide–apatite deposits contain saline brines and have a wide range of Br/Cl molar ratios, from 0.2 to 1.1 × 10⁻³ and δ³⁷Cl values from −3.1‰ to −1.0‰. Leachates from saline fluid inclusions from the Greenstone and Porphyry hosted Cu–Au prospects have Br/Cl ratios that range from 0.2 to 0.5 × 10⁻³ and δ³⁷Cl values from −5.6‰ to −1.3‰. Finally, the Cu–Au deposits hosted by the Nautanen Deformation Zone (NDZ) have Br/Cl molar ratios from 0.4 to 1.1 × 10⁻³ and δ³⁷Cl values that range from −2.4‰ to +0.5‰, although the bulk of the data fall within 0‰ ± 0.5‰.The Br/Cl ratios of leachates are consistent with the derivation of salinity from magmatic sources or from the dissolution of halite. Most of the isotopic data from the Fe-oxide–apatite and Greenstone deposits are consistent with a mantle derived source of the chlorine, with the exception of the four samples with the most negative values. The origin of the low δ³⁷Cl values in these samples is unknown but we suggest that there may have been some modification of the Cl-isotope signature due to fractionation between the mineralising fluids and Cl-rich silicate assemblages found in the alteration haloes around the deposits. If such a process has occurred then a modified crustal source of the chlorine for all the samples cannot be ruled out although the amount of fractionation necessary to generate the low δ³⁷Cl values would be significantly larger.The source of Cl in the NDZ deposits has a crustal signature, which suggests the Cl in this system may be derived from (meta-) evaporites or from input from crustal melts such as granitic pegmatites of the Lina Suite.     

Origin of methane in high-arsenic groundwater of Taiwan – Evidence from stable isotope analyses and radiocarbon dating

Groundwaters in the confined aquifers of the Chianan and Ilan coastal plains of Taiwan are rich in dissolved methane (CH₄). Serious endemic “blackfoot disease”, which occurred in the Chianan plain, especially during AD1950-1970, has been demonstrated to have arisen from drinking highly reducing groundwater with abnormal arsenic and humic substance levels. In order to explore the origin of CH₄ and its hydrological implications, stable carbon isotope ratios (δ¹³C) and radiocarbon (¹⁴C) ages of exsolved CH₄, dissolved inorganic carbon (DIC), and sedimentary biogenic sediments from a total of 34 newly completed water wells at 16 sites were determined. The main results obtained are as follows: (1) The δ¹³C_CH4 (−65‰ to −75‰) values indicate that, except for one thermogenic sample (δ¹³C_CH4=38.2‰) from the Ilan plain, all CH₄ samples analyzed were produced via microbially mediated CO₂ reduction. Many δ¹³C_DIC values are considerably greater than −10‰ and even up to 10‰ due to Rayleigh enrichment during CO₂ reduction. (2) Almost all the ¹⁴C ages of CH₄ samples from the shallow aquifer (I) (<60 m depth) are greater than the ¹⁴C ages of coexisting DIC and sediments, suggesting the presence of CH₄ from underlying aquifers. (3) The ¹⁴C ages of coexisting CH₄, DIC and sediments from aquifer (II) of the Chianan plain are essentially equal, reflecting in-situ generation of CH₄ and DIC from decomposition of sedimentary organic matter and sluggishness of the groundwater flow. On the other hand, both CH₄ and DIC from each individual well of the relatively deep aquifers (III) and (IV) in the Chianan plain are remarkably younger than the deposition of their coexisting sediments, indicating that current groundwaters entered these two aquifers much later than the deposition of aquifer sediments. (4) Each CH₄ sample collected from the Ilan plain is older than coexisting DIC, which in turn is distinctly older than the deposition of respective aquifer sediments, demonstrating the presence of much older CO₂ and CH₄ from underlying strata.     

The evolution of a tropical rainforest/grassland mosaic in southeastern Brazil since 28,000 C yr BP based on carbon isotopes and pollen records

The lack of paleoecological records from the montane Atlantic Rainforest of coastal Brazil, a hotspot of biological diversity, has been a major obstacle to our understanding of the vegetational changes since the last glacial cycle. We present carbon isotope and pollen records to assess the impact of the glaciation on the native vegetation of the Serra do Mar rainforest in São Paulo, Brazil. From ca. 28,000 to  22,000 ¹⁴C yr BP, a subtropical forest with conifer trees is indicative of cool and humid conditions. In agreement carbon isotopic data on soil organic matter suggest the presence of C₃ plants and perhaps C₄ plants from  28,000 to  19,000 ¹⁴C yr BP. The significant increase in the sedimentation rate and algal spores from  19,450 to  19,000 ¹⁴C yr BP indicates increasing humidity, associated to an erosion process between  19,000 and  15,600 ¹⁴C yr BP. From  15,600 ¹⁴C yr BP to present there is a substantial increase in arboreal elements and herbs, indicating more humid and warmer climate. From  19,000 to  1000 ¹⁴C yr BP, δ¹³C values indicated the predominance of C₃ plants. These results are in agreement with studies in speleothems of caves, which suggest humid conditions during the last glacial maximum.     

Diagenetic mineralization in Pennsylvanian coals from Indiana, USA: C/C and O/O implications for cleat origin and coalbed methane generation

Cleats and fractures in southwestern Indiana coal seams are often filled with authigenic kaolinite and/or calcite. Carbon- and oxygen-stable isotope ratios of kaolinite, calcite, and coalbed CO₂ were evaluated in combination with measured values and published estimates of δ¹⁸O of coalbed paleowaters that had been present at the time of mineralization. δ¹⁸O_mineral and δ¹⁸O_water values jointly constrain the paleotemperature of mineralization. The isotopic evidence and the thermal and tectonic history of this part of the Illinois Basin led to the conclusion that maximum burial and heat-sterilization of coal seams approximately 272 Ma ago was followed by advective heat redistribution and concurrent precipitation of kaolinite in cleats at a burial depth of < 1600 m at  78 ± 5 °C. Post-Paleozoic uplift, the development of a second generation of cleats, and subsequent precipitation of calcite occurred at shallower burial depth between  500 to  1300 m at a lower temperature of 43 ± 6 °C. The available paleowater in coalbeds was likely ocean water and/or tropical meteoric water with a δ¹⁸O_water  − 1.25‰ versus VSMOW. Inoculation of coalbeds with methanogenic CO₂-reducing microbes occurred at an even later time, because modern microbially influenced ¹³C-enriched coalbed CO₂ (i.e., the isotopically fractionated residue of microbial CO₂ reduction) is out of isotopic equilibrium with ¹³C-depleted calcite in cleats.     

The role of supergene sulphuric acid during weathering in small river catchments in low mountain ranges of Central Europe: Implications for calculating the atmospheric CO2 budget

The geochemistry of dissolved and suspended loads in river catchments of two low mountain ranges in Central Europe allows comparison of pertinent chemical weathering rates. Distinct differences in lithology, i.e. granites prevailing in the Black Forest compared to Palaeozoic sediments in the Rhenish Massif, provide the possibility to examine the influence of lithology on weathering. Here we determine the origin of river water using the stable isotope ratio δ¹⁸O_H2O and we quantify the geogenic proportions of sulphate from stable isotope ratios δ³⁴S_SO4 and δ¹⁸O_SO4. Particularly in catchments with abundant pyrite, determination of the geogenic amount of sulphate is important, since oxidation of pyrite leads to acidity, which increases weathering. Our results show that spatially averaged silicate weathering rates are higher for the river catchments Acher and Gutach in the Black Forest (10–12 t/km²/yr) compared to the river catchments of the Möhne dam and the Aabach dam in the Rhenish Massif (2–6 t/km²/yr). Correspondingly, the CO₂ consumption by silicate weathering in the Black Forest (334–395 × 10³ mol/km²/yr) is more than twice as high as in the Rhenish Massif (28–151 × 10³ mol/km²/yr). These higher rates for watersheds of the Black Forest are likely due to steeper slopes leading to higher mechanical erosion with respective higher amounts of fresh unweathered rock particulates and due to the fact that the sediments in the Rhenish Massif have already passed through at least one erosion cycle. Carbonate weathering rates vary between 12 and 38 t/km²/yr in the catchments of the Rhenish Massif. The contribution of sulphuric acid to the silicate weathering is higher in the catchments of the Rhenish Massif (9–16%) than in the catchments of the Black Forest (5–7%) due to abundant pyrite in the sediments of the Rhenish Massif. Three times higher long-term erosion rates derived from cosmogenic nuclides compared to short-term erosion rates derived from river loads in Central Europe point to three times higher CO₂ consumption during the past 10³ to 10⁴ years.     

Carbonate precipitation in artificial soils as a sink for atmospheric carbon dioxide

Turnover of C in soils is the dominant flux in the global C cycle and is responsible for transporting 20 times the quantity of anthropogenic emissions each year. This paper investigates the potential for soils to be modified with Ca-rich materials (e.g. demolition waste or basic slag) to capture some of the transferred C as geologically stable CaCO₃. To test this principal, artificial soil known to contain Ca-rich minerals (Ca silicates and portlandite) was analysed from two sites across NE England, UK. The results demonstrate an average C content of 30 ± 15.3 Kg C m⁻² stored as CaCO₃, which is three times the expected organic C content and that it has accumulated at a rate of 25 ± 12.8 t C ha⁻¹ a⁻¹ since 1996. Isotopic analysis of the carbonates gave values between −6.4‰ and −27.5‰ for δ¹³C and −3.92‰ and −20.89‰ for δ¹⁸O, respectively (against V-PDB), which suggests that a combination of carbonate formation mechanisms are operating including the hydroxylation of gaseous CO₂ in solution, and the sequestration of degraded organic C with minor remobilisation/precipitation of lithogenic carbonates. This study implies that construction/development sites may be designed with a C capture function to sequester atmospheric C into the soil matrix with a maximum global potential of 290 Mt C a⁻¹.     

Fluctuation in proteinaceous labile organic matter verified with degradation rate constants of terrestrial biochemical indicators

Biogenic amino acids, taken as representative of organic matter, were analyzed to determine the apparent degradation rate constant in boreal terrestrial sediment. Age determination using ¹⁴C dating gave two rate constants: the initial degradation rate constant for glycine (k_{GLY 1}), the simplest amino acid, was 1.5 × 10⁻³ yr⁻¹ (r = 0.97) until about 2200 yr BP. After the inflection point, the rate constant k_{GLY 2} was 9.1 × 10⁻⁵ yr⁻¹ (r = 0.73). The degradation of amino acids in the labile organic matter in the sediment was markedly affected by rapid processes. After the inflection point, the rate constant profiles for sub-surface amino acids were shown to have discontinuous relationships with sediment age. One pattern which emerged in the vertical distribution is that the biogenic amino acid degradation rate constant k was far greater in the labile organic matter phase than that in the refractory organic matter over the past 10,000 years.     

Isotopic and elemental abundances of copper and zinc in lunar samples, Zagami, Pele’s hairs, and a terrestrial basalt

We used ICP–MS to measure the elemental concentrations and isotopic abundances of Cu and Zn in: nine Ti-rich lunar basalts (10017, 10022, 10024, 10057, 70215, 71055, 74255, 75055, and 75075); size-separated samples prepared by sieving of pyroclastic black glass 74001, orange glass 74022, and the lunar soils 15021, 15231, 70181, and 79221; a basalt from the Piton des Neiges volcano, Reunion Island; two samples of Pele’s hairs from the Nyiragongo volcano, Democratic Republic of Congo, and the martian meteorite Zagami.The isotopic fractionation of zinc in lunar basalts and Zagami is mass dependent relative to a terrestrial standard (JMC 400882B). These and published results imply that lunar, terrestrial, meteoritic, and perhaps martian zinc all come from one or more reservoirs linked by mass-dependent fractionation processes. Relative to terrestrial basalts, Ti-rich lunar basalts are enriched in the heavier isotopes of Cu and Zn: we find for Ti-rich lunar basalts the following ranges and averages ±1 − σ (‰): δ⁶⁵Cu/⁶³Cu ≡ δ⁶⁵Cu, 0.1–1.4, 0.5 ± 0.1‰ (N = 7); δ⁶⁶Zn/⁶⁴Zn ≡ δ⁶⁶Zn = 0.2–1.9, 1.2 ± 0.2‰ (N = 8; 10017 excluded). For two terrestrial samples, we find δ⁶⁶Zn  +0.3‰ and δ⁶⁵Cu  0‰, which are consistent with published values. The differences between the lunar basalts and terrestrial basalts could reflect minor, planetary-scale vaporization or igneous processes on the Moon.Data for size separates of the pyroclastic glasses 74001 and 74220 confirm the well-known surface correlation of Cu and Zn, but modeling calculations reveal no sharp differences between either the elemental ratios or the isotopic composition of grain interiors and exteriors. The absence of such differences indicates that the isotopic compositions for bulk samples are dominated by a light-isotope-rich surface component.Data for size separates of lunar soils also confirm the surface correlation of Cu and Zn, but an enrichment of heavy rather than light isotopes. Averages for bulk lunar soils from this work and the literature are (‰): δ⁶⁵Cu, from 1.4 to 4.1, average 3.0 ± 0.3 (N = 9); δ⁶⁶Zn, from 2.2 to 6.4, average 4.0 ± 0.3 (N = 14). As with the glasses, in all but soil 15231 our data show no strong differences between the isotopic composition of soil sub-samples with small and large grains.The size of the isotopic fractionation inferred for the surface component in the soils is 3× smaller than predicted by a published model of sputtering primarily by solar particles. At the same time, the observed fractionation is larger than predicted by calculations based on a model of micrometeorite impact heating and hydrodynamic quenching. Because impact heating appears unable to explain the observations, we conclude that sputtering must be important even though samples with very large isotopic fractionation of Cu and Zn have not yet been found.     

Carbon isotope chemostratigraphy of a Precambrian/Cambrian boundary section in the Three Gorge area, South China: Prominent global-scale isotope excursions just before the Cambrian Explosion

Carbon isotope chemostratigraphy has been used for worldwide correlation of Precambrian/Cambrian (Pc/C) boundary sections, and has elucidated significant change of the carbon cycle during the rapid diversification of skeletal metazoa (i.e. the Cambrian Explosion). Nevertheless, the standard δ¹³C curve of the Early Cambrian has been poorly established mainly due to the lack of a continuous stratigraphic record. Here we report high-resolution δ¹³C chemostratigraphy of a drill core sample across the Pc/C boundary in the Three Gorge area, South China. This section extends from an uppermost Ediacaran dolostone (Dengying Fm.), through a lowermost Early Cambrian muddy limestone (Yanjiahe Fm.) to a middle Early Cambrian calcareous black shale (Shuijingtuo Fm.). As a result, we have identified two positive and two negative isotope excursions within this interval. Near the Pc/C boundary, the δ¹³C_carb increases moderately from 0 to + 2‰ (positive excursion 1: P1), and then drops dramatically down to − 7‰ (negative excursion 1: N1). Subsequently, the δ¹³C_carb increases continuously up to about + 5‰ at the upper part of the Nemakit–Daldynian stage. After this positive excursion, δ¹³C_carb sharply decreases down to about − 9‰ (N2) just below the basal Tommotian unconformity. These continuous patterns of the δ¹³C shift are irrespective of lithotype, suggesting a primary origin of the record. Moreover, the obtained δ¹³C profile, except for the sharp excursion N2, is comparable to records of other sections within and outside of the Yangtze Platform. Hence, we conclude that the general feature of our δ¹³C profile best represents the global change in seawater chemistry. The minimum δ¹³C of the N1 (− 7‰) is slightly lower than carbon input from the mantle, thus implying an enhanced flux of ¹³C-depleted carbon just across the Pc/C boundary. Hence, the ocean at that time probably became anoxic, which may have affected the survival of sessile or benthic Ediacaran biota. The subsequent δ¹³C rise up to + 5‰ (P2) indicates an increase of primary productivity or an enhanced rate of organic carbon burial, which should have resulted in lowering pCO₂ and following global cooling. This scenario accounts for the cause of the global-scale sea-level fall at the base of the Tommotian stage. The subsequent, very short-term, and exceptionally low δ¹³C (− 9‰) in N2 could have been associated with the release of methane from gas hydrates due to the sea-level fall. The inferred dramatic environmental changes (i.e., ocean anoxia, increasing productivity, global cooling and subsequent sea-level fall with methane release) appear to coincide with or occur just before the Cambrian Explosion. This may indicate synchronism between the environmental changes and rapid diversification of skeletal metazoa.     

Fractionation of silicon isotopes during biogenic silica dissolution

Silicon isotopes have been investigated for their potential to reveal both past and present patterns of silicic acid utilization, primarily by diatoms, in surface waters of the ocean. Interpretation of this proxy has thus far relied on characteristic trends in the isotope composition of the dissolved and particulate silicon pools in the upper ocean, as driven by biological fractionation during the production of biogenic silica (bSiO₂, or opal) by diatoms. However, other factors which may influence the silicon isotope composition of diatom opal, particularly post-formational aging and maturation processes, remain largely uninvestigated. Here, we report a consistent fractionation of silicon isotopes during the physicochemical dissolution of diatom bSiO₂ suspended in seawater under closed conditions. This fractionation acts counter to that occurring during bSiO₂ production and at about half its absolute magnitude, with dissolution discriminating against the release of the heavier isotopes of silicon at an enrichment factor ε_DSi–BSi of −0.55‰, corresponding to a fractionation factor α_30/28 of 0.99945. The enrichment factor did not vary with source material, indicating the lack of a significant species effect, or with temperature from 3 to 20 °C. Thus, the dissolution of bSiO₂ produces dissolved silicon with a δ³⁰Si value that is 0.55‰ more negative than its parent bSiO₂, an effect that must be accounted for when interpreting oceanic δ³⁰Si distributions. The δ³⁰Si values of both the dissolved and particulate silicon pools increased linearly as dissolution progressed, implying a measurable (±0.1‰) change in the relative δ³⁰Si of opal samples whenever the difference in preservation efficiency between them is >20%. This effect could account for 10–30% of the difference in diatom δ³⁰Si values observed between glacial and interglacial conditions. It is unlikely, however, that the inferred maximum possible change in δb³⁰SiO₂ of +0.55‰ would be manifested in situ, as a high mean percentage of dissolution would include complete loss of the more soluble members of the diatom assemblage.     

Feldspathic clasts in Yamato-86032: Remnants of the lunar crust with implications for its formation and impact history

Low concentrations of Th and Fe in the Yamato (Y)-86032 bulk meteorite support earlier suggestions that Y-86032 comes from a region of the moon far distant from the Procellarum KREEP Terrain (PKT), probably from the lunar farside. ³⁹Ar–⁴⁰Ar, Rb–Sr, Sm–Nd, and Sm-isotopic studies characterize the chronology of Y-86032 and its precursors in the mega regolith. One of the rock types present in a light gray breccia lithology is an anorthosite characterized by plagioclase with An 93, i.e., more sodic than lunar FANs, but with very low ⁸⁷Rb/⁸⁶Sr and ⁸⁷Sr/⁸⁶Sr similar to those of FANs. (FAN stands for Ferroan Anorthosite). This “An93 anorthosite” has Nd-isotopic systematics similar to those of nearside norites. A FAN-like “An97 anorthosite” is present in a second light-colored feldspathic breccia clast and has a more negative ε_Nd value consistent with residence in a LREE-enriched environment as would be provided by an early plagioclase flotation crust on the Lunar Magma Ocean (LMO). This result contrasts with generally positive values of ε_Nd for Apollo 16 FANs suggesting the possibility of assymetric development of the LMO. Other possible explanations for the dichotomy in ε_Nd values are advanced in the text. The Y-86032 protolith formed at least 4.43 ± 0.03 Ga ago as determined from a Sm–Nd isochron for mineral fragments from the breccia clast composed predominantly of An93 anorthosite and a second clast of more varied composition. We interpret the mineral fragments as being predominatly from a cogenetic rock suite. An ³⁹Ar–⁴⁰Ar age of 4.36–4.41 ± 0.035 Ga for a third clast composed predominantly of An97 anorthosite supports an old age for the protolith. Initial ¹⁴³Nd/¹⁴⁴Nd in that clast was −0.64 ± 0.13 ε-units below ¹⁴³Nd/¹⁴⁴Nd in reservoirs having chondritic Sm/Nd ratios, consistent with prior fractionation of mafic cumulates from the LMO. A maximum in the ³⁹Ar–⁴⁰Ar age spectrum of 4.23 ± 0.03 Ga for a second sample of the same feldspathic breccia clast probably reflects some diffusive ⁴⁰Ar loss. Lack of solar wind and lunar atmosphere implanted Ar in the light gray breccia clast allows determination of an ³⁹Ar/⁴⁰Ar age of 4.10 ± 0.02 Ga, which is interpreted as the time of initial brecciation of this litholgy. After correction for implanted lunar atmosphere ⁴⁰Ar, impact melt and dark regolith clasts give Ar ages of 3.8 ± 0.1 Ga implying melt formation and final breccia assembly 3.8 Ga ago. Some breccia lithologies were exposed to thermal neutron fluences of 2 × 10¹⁵ n/cm², only about 1% of the fluence experienced by some other lunar highlands meteorites. Other lithologies experienced neutron fluences of 1 × 10¹⁵ n/cm². Thus, Y-86032 spent most of the time following final brecciation deeply buried in the megaregolith. The neutron fluence data are consistent with cosmogenic ³⁸Ar_cos cosmic ray exposure ages of 10 Ma. Variations among differing lithologies in the amount of several regolith exposure indicators, including cosmogenic noble gas abundances, neutron capture induced variations in Sm isotopic abundances, and Ir contents, are consistent with a period of early (>3.8 Ga ago) lunar regolith exposure, subsequent deep burial at >5 m depth, and ejection from the moon 7–10 Ma ago.     

Hydrochemistry and isotope compositions of groundwater from the Shihongtan sandstone-hosted uranium deposit, Xinjiang, NW China

Groundwaters and surface water in the Shihongtan sandstone-hosted U ore district, Xinjiang, NW China, were sampled and analyzed for their major-, and trace element concentrations and oxygen, hydrogen, boron and strontium isotope compositions in order to assess the possible origins of the waters and water–rock interactions that occurred in the deep aquifer system. The waters in the study district have been grouped into three hydrochemical facies: Facies 1, potable spring-water, is a pH neutral (7.0), Na–Ca–HCO₃ type water with low total dissolved solids (TDS; 0.2 g/l, fresh) and has δ¹⁸O of − 8.3‰, δD of − 48.2‰,δ¹¹B of 1.5‰, and ⁸⁷Sr/⁸⁶Sr of 0.70627. Facies 2 groundwaters are mildly acidic to mildly alkaline (pH of 6.5–8.0, mean 7.3), Na–Ca–Mg–Cl–SO₄ type waters with moderate TDS (8.2 g/l–17.2 g/l, mean 9.3 g/l, brackish) and haveδ¹⁸O values in the − 5.8‰ to − 9.3‰ range (mean − 8.1‰), δD values in the − 20.8‰ to − 85.5‰ range (mean − 47.0‰),δ¹¹B values in the + 9.5‰ to + 39.1‰ range (mean + 17.1‰), and ⁸⁷Sr/⁸⁶Sr values in the 0.70595 to 0.70975 range (mean 0.70826). Facies 3, Aiting Lake water, is a mildly alkaline (pH = 7.4), Na–Ca–Mg–Cl–SO₄ type water with the highest TDS (249.1 g/l, brine) and has δ¹⁸O of − 2.8‰, δD of − 45.8‰,δ¹¹B of 21.2‰, and ⁸⁷Sr/⁸⁶Sr of 0.70840. The waters from the study district show a systematic increase in major, trace element and TDS concentrations and δ¹¹B values along the pathway of groundwater migration which can only be interpreted in terms of water–rock interaction at depth and strong surface evaporation. The hydrochemical and isotopic data presented here confirm that the groundwaters in the Shihongtan ore district are the combined result of migration, water–rock interaction and mixing of meteoric water with connate waters contained in sediments.     

Variations of stable isotopes with depth in regolith calcite cements in the Broken Hill region, Australia: Palaeoclimate evolution signal?

Twenty two samples of calcretes from seven depth-profiles in the Menindee catchment, Broken Hill region, Australia were analysed for their inorganic and organic carbon contents and inorganic carbon and oxygen isotopes. The organic carbon content is very low (from 0.06 to 0.31 wt.%) while inorganic carbon (carbonate) is up to 3.9 wt.%. Both δ¹³C and δ¹⁸O become more positive closer to the surface. Carbon isotopes vary from − 8.5‰ to −5.5‰ PDB. Oxygen isotopes vary from − 6‰ to − 1.8‰ V-PDB. Depth-related δ¹³C and δ¹⁸O variations correlate over at least 15 km and show no significant variation along the flow path. δ¹³C values increase by 3‰ and δ¹⁸O values increase by 4‰ with decreasing depth in a 1.40 m thick soil profile. The variation is interpreted to indicate an increasingly elevated air temperature, greater water stress and subsequently an aridification of the area through time. The Broken Hill calcrete data confirm that climatic evolution can be deduced from isotopic series and be applied successfully to the Broken Hill region.